Table ii



Dec. 15, 1959 INVENTORS EVERETT E.GILBERT SILVIO LGIOLITO BMW il)ATTORNEY United States Patent O KETONIC CmClmO PESTICIDE AND METHOD FORCOlVATTING NOXIOUS ORGANISMS THERE- Everett E. Gilbert, Morris Township,Morris County, NJ., and Silvio L. Giolito, Whitestone, N.Y., assignorsto Allied Chemical Corporation, a corporation of New York Original No.2,616,825, dated November 4, 1952, Serial No. 196,121, November 17,1950. Application for reissue August 19, 1957, Serial No. 679,115

Matter enclosed in heavy brackets appears in the original patent butforms no part of this reissue specification; matter printed in italicsindicates the additions made by reissue.

This invention relates to a new pesticidal composition comprising[decachlorotetrahydro 4,7 methanoindeneone] a ketonic compound havingthe empirical formula CwClIoO and to a method for combating noxiousorganisms therewith.

The [decachlorotetrahydro 4,7 methanoindeneone] CwClloO ketonecompositions of our invention are useful in combating a wide variety ofnoxious organisms including insects and their larvae of the Hymenoptera(flies), Lepidoptera (moths), Coleoptera (beetles) and Orthoptera(grasshoppers) species, and also in combating crop-attacking fungi.

The compositions of our invention comprise essentially [adecachlorotetrahydro4,7-methanoindeneone] the ketone CwCllO, which isthe hydrolyzed reaction product of hexachlorocyclopentadiene with eithersulfur trioxide or a halosulfonic acid, usually in hydrate form, whichmay be applied alone or in association with a spray or dust carriermaterial in any suitable manner adapted to combat the particularorganism to be controlled. As a spray or impregnant, the solid[decachlorotetrahydro- 4,7-methanoindeneone] ketone compound mayconveniently be dissolved or dispersed in any standard liquid carrier,such as kerosene or thelike. As a dust, it may be mixed with a suitablefinely divided solid material, such as clay or the like. It may readilybe applied from solution in solvents in which it is soluble as morefully set forth hereinafter, for example in acetone, lower aliphaticalcohols, or in mixtures of such alcohols with water or kerosene.Application of [decachlorotetrahydro- 4,7-methanoindeneone] the CMCINOketone in liquid solution formV is especially adapted to moth-proofingof fabrics and to control of houseflies and the like, while applicationin the form `of dusts or liquid sprays may conveniently be used in itsapplication to vegetable crops and the like, to control infestations ofinsects' or fungi, Whereas grain or flour infesting organisms may becontrolled by the addition of small quantities of undiluted[decachlorotetrahydro-4,7-methanoindeneonel CNCIMO ketone directly tothe grain material.

The [decachlorotetrahydro 4,7 methanoindeneone] hydrate of thehydrolyzed hexachlorocyclopentadene S03 reaction product ischaracterized by the following chemical analysis:

y 11.2.24,749 Reissuecl Dec. 15, 1959 ICC l at 140 C. at l-1.5 mm. of Hgpressure, l0-15% of its weight sublimes in three hours. It sublimes withsome decomposition when heated in the open atmosphere to 300 C. It isreadily soluble in acetone, lower aliphatic alcohols, ethers and thelike, and also nitrobenzene, and sulfuryl chloride. It is somewhat lesssoluble in benzene, toluene, hexane and petroleum ether, but issufficiently soluble in warm hexane to allow the use of this material asa recrystallizing solvent if desired. It is virtually insoluble in coldWater and only slightly soluble (less than 0.4%) in boiling water. Ittends to gel upon separation by cooling, from hot solutions inhydrocarbon solvents. A satisfactory recrystallizing solvent is %90%aqueous ethanol from which gelation does not occur. It usually exists asa crystalline hydrate when exposed to atmospheric conditions and isuseful for insecticidal, etc., purposes in hydrate form.

The [decachlorotetrahydro 4,7 methanoindeneone] ketonic CmClmO compoundis soluble in, and relatively stable toward, strong caustic solutions,such as sodium,

potassium and calcium hydroxides. This stability towards causticmaterials is of advantage in its application as a pesticide incombination with lime and other alkaline agricultural chemicals, and inthis respect it is superior to benzene hexachloride (BHC) anddichlorodiphenyltrichloroethane (DDT) l which decompose readily oncontact with ,alkalis. Furthermore, being volatile under normally`atmospheric conditions only rat temperatures considerably above thoseusually encountered in use, it has a high residual insecticidal activityand because of its limited solubility in hydrocarbon solvents, it isconsiderably more resistant in dry cleaning than DDT, which isdesignated above in the use of this compound as a moth-proofing agent.

In the accompanying ligure, the several lines represent in carbondisulfide solutions of samples of dilerent degrees hydration; dottedline A being the record of substantially anhydrous material (0.10% or0.03 mol H2O); solid line B being the record of a slightly hydratedsample (0.84% or 0.24 m01 H2O); while solid line C is the record of anessentially monohydrated sample (2.86% or 0.8 mol H2O). The threespectrograms are considered substantially identical. Solid line D s thespectrogram of the CS2 solvent. It will be noted that the ketonic CmClMOcompound, as shown in the drawing, exhibits, when anhydrous, (A) aninfrared spectrogram which has characteristicabsorption peaks at thewave lengths 5.5; 8.5; 8.9,' 9.6; 11.6; 12.2; 12.8; 15.2 and 15.6microns, and, when hydrated (especially C), has characteristicabsorption peaks at wave lengths 2.8; 8.2; 8.6; 8.7; 9.4; 10.1; 10.5;10.8; 11.8; 12.6; 14.3; 15.2 and 15.7 microns.

These infrared spectrograms were prepared on a standard infraredrecording spectrophotometer designed for measuring and recording theinfrared transmission of solids, liquids? and gases, comprising a doubleinfrared beam which scans the spectrum through the wave length range 2.0to 16 microns, one part of the beam passing throughthe sample understudy, the other passing through a compensating cell. If the sampleunder study absorbs radiation, the two beams become unequal. Themagnitude of this inequalityeis a measure of the transmission of thesample of the particular wave length, and the record of thesedifferences Within the range of wave lengths scanned is the infraredspectrogram, recorded as an ink drawn lineon a chart graduated inpercent transmission as ordinates and in wave length as abscissae.

Solid samples, such as the compound of our invention and the relatedcompounds described, are conveniently measured in solution. VThespectrograms shown in the figures were all measured by dissolving 0.5gram of the solid in carbon disulfide and diluting to 10 ml. with thesolvent. A small amount of thesolution was then introduced linto aliquid cell with sodium chloride Windows and sealed. Thecell was placedin the spectrophotometer in the path of one of the beamsasdescribedabove.

The infrared spectrograrn `of any chemical compound serves asanaccuratemeans for identifying `the compound. It has been compared with,a Lhuman .fingerprint in its ability to identify a compoundlwithcertainty. The characteristic reproducibility of theinfraredspectrogramof a given `Compound is due to the facts that when a molecule is excitedby infrared radiation it absorbs energy to a greater degree at somewavelength lthan -at others, `and that the amount of absorption dependson the configuration and upon the linkages of the atoms composing themolecule. Accordingly, the compound vis identified and characterizedwith certainty by its infrared spectrogram.

The new pesticidal composition of ,our inventio-n may be prepared by anysuitable process, for yexample by condensing two molecules ofhexachlorocyclopentadieue with the aid of sulfur trioxide to form ahexachlorocyclopentadiene reaction product and hydrolyzng the reactionprodanoindene-1-one.

While the overall reaction in the methodsvof preparation described aboveproceeds from ythe same starting material to the same end product whencarried out using the S03 treatment and when using the halosulfonic acidtreatment, the reaction mechanisms [probably/1 may differ but are notclearly understood [and are believed to proceed somewhat as illustratedbelowz] wherein X=chloriue or fluorine In carrying out the process forpreparing the [decachlorotetrahydro 4,7 methanciindenec'me compound]CJOCIMO ketone above described, according to the procedure whereinsulfur trioxide is used, hexachlorocyclopentadiene and sulfur trioxideare mixed by charging them, either simultaneously or separately, to areaction vessel. After mixing the reactants, the charge may be digestedfor a short period, suicient to condense two molecules ofhexachlorocyclopentadiene and to form a liquid reaction product ofhexachlorocyclopentadiene and sulfur trioxide. Y

The liquid Soa-hexachlorocyclopentadiene reaction product thus formed isthen hydrolyzed to the [decachloromethanoindeneone] ketone, by drowningthe reaction product in a-relatively large volumeof an aqueous drowningmedium," preferably an alkaline aqueous medium, for example in at leastabout volumes of drowning medium per volume of reaction product.

After'addition of the reaction product to the drowning medium iscomplete, the mixture may be digested for a short additional period, forexample a half hour to insure completion of the hydrolysis.

safari should be sufficient to bring the mixture preferably toneutrality, or to a very slight alkalinity not exceeding about 0.05%NaOH, as indicated by a pH of 7-8.

After neutralization, the charge is agitated, preferably at atemperature between about 90 C. and about 95 C.,

for about a half hour while ,maintaining the mixture at the neutralpoint or slightly on the alkaline side.

The mixtureis then cooled, for example to; roomA temperature to insurerelatively complete precipitation of the product, leaving in solutionthe salts formed in the neutralization step, e.g.a1kali metal orammonium chloride and sulfate.

Separation of the'lprecipitated product may be effected TABLE 1 V WeightMols H10 Sample No. Percent per Mol Comment H2O Anhydrous Compound -0 0Theory for anhydrous compom.. .V. -.3.54A .Q 1 Theory formunohydrate.

6.84 .2 Theory for dihydrate. 4.76 l. 36 Dried 18 hours ai; 90C.'1.'.:1;.70 1.0.47 .Dried 72 hours at 90 C. 10.90v 3.33 Dried 72 hoursat,27 0.. 3.02 .,0. .85 V

In carrying out the process fr preparing the[decachloi'otetrahydromethanoindeneone] ketomc CMClmO compound of ourinvention according to the procedure wherein a halosulfonic acid, suchas-uosulfonic acid or chlorosulfonic acid, is used as the condensingagent, hexachlorocyclopentadiene and the halosulfonic acid are mixed ina reaction vessel for a period sufficient to form a solid reactionproduct of hexachlorocyclopentadiene and halosulfonic acid.

The solid hexachlorocyclopentadiene-halosulfonic acid reaction productthus formed is then hydrolyzed to the[decachlorotetrahydromethanoindeneone] ketone of our invention in arelatively large volume of an aqueous drowning medium.

The halosulfonic acid used as condensing agent to form thehexachlorocyclopentadiene-halosulfonic acid reaction product may bechlorosulfonic acid or tluosulfonic acid, used either alone, ordissolved in asolvent which is inert to the reaction such astetrachloroethylene. y

The temperature of the initial-condensation reaction may be somewhathigher than that used when S03 is the condensing agent and may becarried as high as 140 C., if desired, and thus effect a reduction inthe time necessary for completion of the reaction over that necessarywhen lower temperatures are employed. Usually temperatures between aboutC. and about 120 C. are satisfactory to eifect completion of thecondensation reaction in from about 5 to about 2 hours, respectively.

The molar ratio of halosulfonic acid to hexachlorocyclopentadiene forgood yields of reaction product should be at least about 1:2, and wehave found that ratios between about 1.25 :2 and about 8:2 aresatisfactory. The hydrolysis of thehexachlorocyclopentadiene-halosulfonic acid reaction products to[decachlorotetrahydromethanoindeneone] th'e ketone may be effected byheating the reaction product with an aqueous caustic alkali solution, awater solution alone being ineffective to accomplish completehydrolysis, probably because of the low solubilities of these reactionproducts in Water. In the case of the chlorosulfonic acid product,hydrolysis may be carried out in aqueous lower aliphatic alcoholsolution which appears to impart s uflicient solubility to the reactionproduct to promote hydrolysis. However, the uosulfonic acid react-ion'product requires 4at least some alkali in the solution for'adequatehydrolysis. Temperatures .at which theH hy'drolysesm are. carried outare not particularly critical, but preferably should be at least about30? C., and temperatures between about 60 C. and about 90 C., that is,temperatures in the vicinity of the boiling points of the loweraliphatic alcohols are satisfactory. i i A In general, no digestion stepis necessary following the hydrolysis of thehexachlorocyclopentadiene-halosulfonic acid reaction products as the[deca'chlorotetrahydromethanoindeneone product] ketom'c CIUCIMOcompOuna' precipitates readily-from the reaction mixture uponacidification with .aqueous min-eral acids.

The toxicity characteristics of our new[decachlorotetrahydro-4,7-methanoindeneone (designated DTMO in v-thetables)] C1-Cl100` ketone against various pest organisms are indicatedby the following tests, results of which are tabulated below...

1 TABLE I! Toxicity ofl IEDEMOT! @10611.09 ketone to. houseios ys-DD'IETv Y Qur. new compound. was; compared, with,.2,3.4,5 ,6.718.8-ootechlorfofotrahyd@4J-modload@ano Chlordauejlagainst ies in. tests4 ix1 which panels. were. sprayed; with Solutions Qfthewxanfe with resultsShown. in Table III- TABLE [Il Toxicity of; EDIMOJ. 610.61m@ ketone to.houseios vs'.

The tests recorded, in Table; compare [DTMQ] CMCIMO withLDD'I'(both,as.5 dusts) againstisoluthern armyworms. and Mxoen. been beetlelarvae TABLE. LV

Toxicity. of [DTMQI: CaClwQ ketone to. end bosnhoetlesvsf. DDI

i Percent Kill Against- Treatment4 .'Armyworms B; B. Larvae [n'rMo]Cmczwo Kameez, l 10o. 50.0 DDT, 3%; Clay, 97% 100 66.' 6

Results of American` cockroaches are. shown in Table V. below, using twohundredI mg. of dustV` for each, test.

Results ony Stored. iaseots.. i-.ebean. weoviLand confused our beetleare shown in'fljable 8 TABLE v1 ToxicityI ofE [lD.:'I:`lStGII. 61061.10@ketone to. insects Carpet beetle larvae.. are customarily, used ineyaluang moth-proofing characteristics of; woolens. sinceV theyA are Alarvae of.. the Same genorattype as. those, of the. clothesmoth-211.1111161' not only are in general. Sigmfoantly moreresistanttotoxicants than, theclothes rnvoth,1.alrva`e.,y blutareactually. responsible for a largel proportion ofthe. damage tp, woolenmaterials loosely, characterized ,asA mothk damage. Moth-proong testsusing carpet beetle larvae.. I Sftest organisms were carried out` bysoaking woolens'watches in 1% asetone Solution ofv our.Edeoaohlorotetrahydro.- methouoindeuoonel CwClwQ` ketone, and DDI forcon1pa1jiso1 1.` The swatches` werel dried, weighedY to deter,- mine`deposit, dry cleaned as indicated to.` determine the tenacity of itsadherence to cloth,1ande;gpovs,ed tolarvae before and after cleaning,withF results. shown in TableVII.

TABLE VII` Toxicrtyof [DTMO] CMC-21100 ketone to carpet beetles vs.`DD IOhsenvations. l'egcent: No.I Percent After- Th1-ees naposim 1 Evry.r1Deposit. No Weeks; Treatment: ou. .Cleon-H ,f After. .Let-- Swatch nings f Dryv vae 1 Gieanmg f Daad. Roode [DTKM'olCmOlwO Ketting 1%111Acetone:

.2,8 2 2.1 2o 2o`v Trees, 2.5 2 LefA 2o- 2o Do. 2.2 1 2. 2., 20; 20j`None. 2.4 1y 2.11AV 2o 19, Trace. 2.8 0 20- 20 None 2.7 2 1.7 20 7Trace. 2.5 2 1.9 2o 13 Do. 2.5 1 1.6 2o 5 Do. 3.0 1` 1.8 20 14 Do. 2.30- 20 2D None It is evident from the results shown in Table VII that notonly isour compound more destructive to the carpet beetle larvae thansUDDT, but that it is more resistant than DDT to dry cleaning, being aneffectivetoxicant even aitor. at least. twoloanings- The prolongedAinsecticidal etectiveness of our cornpound is indicated by the resultsrecorded in Table VIII. In the reported tests, bean plants were dustedwith. 3% dusts of our compound andr o f Chlordane respectively, theninfested with 6th instar southern armyworms. at the time intervalsindicated.

l ITABLE vm l Residual insecticidal activity of [DTMO] CmClmO A ketonevs. Chlordane l 1d y TABLE XI Toxicity of [DTMO] CMCINO ketone toseveral potato infesting insects 5 Age .oi' Deposit Percent l No. oiOrganisms Kill t t Caught by Sweeping After Fourth Treatment Bu. lInsecticide per ig F1 P1 1; L t we ea an ea [DTMO] CnC'liaQkctone,3%Dust 100 lo Beetle Bugs Hop 100 pers Chlofdme .3% Dust 13.3 [D'IMo]cmozmo Kanne oomp.1+

0 Test Insecticide 2 5 3 2 304 Test Insecticide l 61 15 3 220.Fungicidal properties of.our compound against early blight of potatoes(Alternaria solani) are shown by the results set forth in Table IX ofiield tests in which our compond, mixed with a test insecticide, wasapplied to potatoes in nine spray applications in the standard mannerVat about two week intervals in comparison with the results obtained withthe test insecticide alone.

. 1 25% [DTMO] CnClmO Keione+75% Clay-5 lb./100 gals. oi water. TestInsecticide-(25% dichlorodiphenyltrichloroethaue-i-S% para nitro phenyldlethyl thiono phosphate in a petroleum emulsion) at the r'ate of 1 lb.of emulsion per S00 gals. of water.

Il l lb./400 gals.

v Field tests carried outon a Montana range on which grasshoppersaverage l2-15 per square yard showed the results listed in Table -X whenthe toxicantslisted were applied to the range with a power turbineblower at the indicated raterper acre.4 t

i TABLE -x TOXCY Of. CNCIMO keffleto grasshoppers vs. Chlordane 1Percent Kill Pounds vInsecticide -Applied PerAcre 24 hrs. 72 hrs.

[DTM0]C|C'l100Kctone- 1 60 100 "Chlordane" `1 75 Our compound, mixedwith the same test insecticide described in Table IX, was applied topotatoes in New Hampshire fields in comparison with the same testinsecticide used alone. The potatoes were given four spray treatments atabout two week intervals with each composition. Seven days after thefourthV treatment, the insects were dislodged from the plants by thecustomary sweep technique, caught and counted. Table XI shows therelative number of the various insects remaining after the treatmentsand also shows the improvement in yield of potatoes after treatment withour compound over that when the test insecticide alone was used.

1 25% [DTMO] 01001100 Kantone-131591; Clay-6 lbs./800 gals. of water. I;

2 25% DDT and 3% p-nitrophcnyl diethyl thiono phosphate in petroleumemulsion-1 lb. of emulsion per 800 gals. of water.

3 Asl 1b.]400 gals. of water.

While the above describes the preferred embodiments of our invention, itwill be understood that departures may be'made therefrom within thescope of the specificaactive ingredient a[decachlorotetrahydro-4,7methanoin` deneone] ketonic compound having theempirical formula CmClwO characterized by the property of sublimingwithA some decomposition when heated in the open atmosphere to 300 C.;by solubility in acetone, lower aliphatic alcohols, ethers, nitrobenzeneand sulfuryl chloride and by insolubility in cold water, and bysolubility in and stability towards strong alkali metal hydroxidesolutions and having, when anhydrous an infrared spectrogram which hascharacteristic infrared absorption peaks at the wave' lengths 5.5; 8.5;8.9; 9.6; 11.6; 12.2; 12.8; 15.2 and 15.6 mir'cons, and when hydrated,having characteristic infrared absorption peaks at the wave lengths 2.8;8.2; 8.6; 8.7; 9.4; 10.1; 10.5; 10.8; 11.8; 12.6; 14.3; 15:2 and 15.7microns; and a pesticidal adjuvant therefor. i

2. A pesticidal composition as defined in claim l wherein said activeingredient is dissolved in a pesticidal adjuvant comprising a liquidorganic solvent for the active ingredent. I 3. A pesticidal compositionas deiined in claim 1 wherein said active ingredient is dissolved in apesticidal adjuvant comprising a hydrocarbon liquid solvent for ltheactive ingredient. J j:

4. A pesticidal composition comprising. as its essential activeingredient a [decachlorotetrahydro-4,7-rnethanoin deneone] ketonir,`compound having the empirical formula C C1100 characterized by theproperty of sublming with some decomposition when heated in the openatmosphere to 300 C.; by solubility in acetone, lower aliphaticalcohols, etlzers, nitrobenzene and sulfuryl chloride and byinsolubility in cold water, and by solubility in and stability towardsvstrong alkali metal hydroxide solutions and having, when anhydrous, Vaninfrared spectrogram whchhas characteristic'` infrared absorption peaksat the wave lengths 5.5;l 8.5;`8.`9; 9.6;' 11.6; 12.2; 12.8; 15.2 and15.6 microns; and when hydrated, having characteristic infraredabsorption peaks at 2.8; 8.2; 8.6; 8.7; 9.4; 10.1; 10.5; 10.8; 11.8;12.6; 14.3; 15.2 and 15.7 microns, admixed with a water-insoluble soliddiluent as pesticidal adjuvant therefor, both lin finely divided form.

5. A pesticidal dusting powder comprising a minor proportion of a finelydivided [decachlorotetrahydro-4,7 methanoindenone] ketonic compoundhaving the empirical formula CMCIMO characterized by the property ofsubliming with some decomposition when heated in the open atmosphere vto300 C.; by solubility in acetone, lower aliphatic alcohols, ethers,ntrobenzene and sulfuryl chloride and by nsolubility in cold water, andby solubility in and stability towards strong alkali metal hydroxide1.1. solutions and having, when anhydrous an infrared spectrogram whichhas characteristic infrared absorption peaks at thev wte lengths 5.5;8.5; 8.9; 9.6;, 11.6,- 12,.,2; 12.8; 15.2 and 15.6 mircons;I and whenhydrated, having characteristic infrared'absorpton peaks at the wavelengths 2.8; 8.2; 8.6'; 8l7'; 9.4,' 10.1; 10:5; 10.8; 11.8; 1216; 14:3;15.2 and 1557"rnirrons4 asits; essential active ingredient admixed with,a` major propontion of nely divided clay as pesidal adjuvant therefor;

6. A method, fon combating noxious [pest] insect and fungus` osganismswhich comprises contacting said orggitiismswith a, compositioncontaining as an essential active ingredient a.[1decachlorotetrahydro-4,'Z-methlanoindeneone] ketonic compoundhavingthe, empirical formula C'MCIMO characterized* by the property t ofsubliming withsome'd'ecompostion when heated" in the open atmosphere to300' C.;- by solubility. in. acetone, lower aliphatic alcohols, ethers,nitrobenzene; and. sulyurylV chloride andy byy insolubility in coldwater, and by solubility in and stability towards strong alkali metalhydroxide solutions and having, when,anhydrous,y anv infraredlspectrogram which has characteristic infrared; absorption peaks atl the'wave lengths 5.5.18.5; 8.9; 11.6; 12.2; 128'; 15,;2and[15.6' microns,and, when hydrated; having characteristic infrared absorption peaks atthe wave lengths 2.8;l 8:2; 8.6; 8.7;, 9.4; 10,1;f 10.5; 10,8;` 11.8,-`12.6,- 14.3,- 15.2 and15.7 microns.

7. A method for combating insects of' the hymenoptera Species. which.,comprises Contacting Said insects.A with a composition containingyasan'essential'activc ingredient-f a [dscachlarotetrahydm 4.7methanoindenonel ketonic compound having the empiricalformul'a CmCliQOcharacterized by theY property of' subliming with some decompositionuwhenV heated inthe open atmosphere to 300 C'.; by `solub'ility inVacetone,Y lower aliphatic alcoholsgethers,` `nitrobenzene and sulfuryl;chloride and' by insolublityin cold water, and by solubility in and,stability towards stromaY alkali metal,` hydroxide solutions and having.when anhydrous, anq infrared spectrogram which has characteristicinfrared. absorption peaks at the wave lengths 5.5,; 8.5; 8.9; 9.6;11.6,,12.2,71 2,8; 15.2` and']5.`6microns,and; when. hydrated,y havingcharacteristic infrared absorption aeak's. at.l the wave lengths 2.8;8,2,-` 8:8;-A 8:7',- 9.4; 10.1; 10,5; 10,3.'f 1.1.8.1 12.6; 1.4.3; 15.2Land'15t7i microns.

8. A method for combating insects of' the lepidoptei'a Species which.comprises contacting. said. ixiststsY witha ampositioncntaining. @sanessential activeY ingtediet a [decchlormctrahydro 4.,.7;methanoindgeneonel ketoaic compound having the empirical 'formula-Cgt'wp charac tea'zqd. by. the. Rionero. af `Syblimim;` -wili Same.dCQmposition when heated in the open atmosphere to 300 C.; by.solubility inI acetone, lower aliphatic alcohols, ethers, ainobenzeneand sulfaryl. chloride-v ami` by iasolability in cold. water, and' blySolubility in and Stability towards strong` alkali metalfhydroxidesolutionsl and having,-` when anhydrous an` infrared spectrograrn whichhas characc, infraredabsorption. peaks at the wave lengths- 5.5,' 8.5;:8.9; 9.6,' 112,6; 12.2; 12.8; 15.2 and.'15.6' microns, and when,hydrated, l, having characteristic infrared absorption aeaks at. the`wavelengths 2.8.'. 8.2; 826;.y 8.7; 9:4; 10.1:

9. A method for combating insects of the coleoptera species whichcomprises contacting said insects with a composition containing as anessentialv active ingredient a [decachlorotetrahydrq- 4173-methanoindeneonel lcetonic compound having the empirical formula CmClmOcharacterizedby ther pr'opertyofn sublim'ingwithv some decompositionwhen. heatedi in the open atmosphere to 300 C.; by solubility inacetone, lower aliphatic alcohols, ethers, nitrobenzene and sulfurylchloride and by insolubility in cold water, and'by. solubility in andstability towards strong alkali. metal= hydroxide solutions and'having,when anhydrous, an infraredspectrogram which has characteristic infraredabsorption peaks at the wave lengths 5.5.; 8.5; 8.9,' 96.11116.; 112112;12.8; 15 .2 and 15.6 microns, and, when. hydrated.. having,lcharacteristic infrared absorption peaks at the wave lengths 2.8; 8.2;8.6; 8.7; 9.4; 10.1; 10.5; 10.8; 11.8; 12.6; 14.3; 15.2 and 15.7microns.

10. A method.y forA combating insects*1 of the.` onthoptera specieswhich` comprises; contacting said insects: with a compositionlcontainingy as. an essential active; ingredient: a[decachlorotetrahydro457 .methanoindeneonel ketonif; compound having..they empirical formula @MC500 char.'- actenized by. the property ofsubliming with some.l decomr. position when heatedirr, the openatmosphere; to. 300' C.; by solubility in acetone, lower aliphaticalcohols, ethers, nitrobenzene and sulfuryl chloride and by insolubiltyin cold water, and by solubility." in and stability towards strongalkali metal hydroxide solutions and having, when anhydrous; anyinfrared spectrogram which` has characteristie infrared absorption peaksatthe wavelengths 5 .5; 8.5; 8.9; 9.6;, 111.6; 12.2; 12.8; 15.2 and 15.6 microns, and, when hydrated; having characteristic infraredabsorption peaks at thewave lengths 2.8; 8.2; 8.6; 8.7; 9.4; 10.1; 10.5;10.8,' 11.8; 112.6; 14.3; 15.2 and 15.7 microns.

11. A method' for combating fungi' which comprises contacting saidfungi' with a composition containing asan essential active ingredient. a[dccachlorotetrahydro-4,7- methanoindeneoneIl, ketonic compound havingVthe empirical formula 61001100fcharacterized.V by thefproperty ofsubliming with some decomposition'when.heated in the open atmosphere to300 C.; by solubility; in. acetone, lower aliphatic alcohols, ethers,nitrobenzene and sulfuryl chloride and by insolubility in cold water,and by solubility inand stabilityv4 towards.strong-alkalimetalvhydroxide solutionsand!- having, when anhydrous, antinfrared spectrogram whichV has characteristicy infraredf absorptionpeaks at the wave lengthsly .5; SI5? 829," 9:61 121.2; 12.8; 15.2 and15.6 microns, and; whenflhydrated'; having characteristic infraredabsorption peaks at the wave lengths 2.8; 8.2; 8.6; 8.7; 9.4; 10.1;10.5; 10.8; 11.8; 12.6;

` 14.3; 15.2 and 15.7 microns:

References Cited n-,the` leofthisipatent on theorigirial` patent-1UNITED- STA-TES- PATENTS.

Hyman May 9, 1950 Hyman ,..,..Aug. 15, 1950 OIHER.

